CN105714590B - Separating lignin and hemicellulose and the method for reclaiming alkali lye from black liquid - Google Patents
Separating lignin and hemicellulose and the method for reclaiming alkali lye from black liquid Download PDFInfo
- Publication number
- CN105714590B CN105714590B CN201610233203.4A CN201610233203A CN105714590B CN 105714590 B CN105714590 B CN 105714590B CN 201610233203 A CN201610233203 A CN 201610233203A CN 105714590 B CN105714590 B CN 105714590B
- Authority
- CN
- China
- Prior art keywords
- lignin
- hemicellulose
- alkali
- black liquid
- liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C11/00—Regeneration of pulp liquors or effluent waste waters
- D21C11/04—Regeneration of pulp liquors or effluent waste waters of alkali lye
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
- C07G1/00—Lignin; Lignin derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/14—Hemicellulose; Derivatives thereof
Abstract
The present invention discloses separating lignin and hemicellulose from black liquid, and the method for reclaiming alkali lye, includes the one-level ultrafiltration of black liquid（15 ~ 25KD ceramic filtration membranes）Retain out hemicellulose, two-stage ultrafiltering（1 ~ 5KD ceramic filtration membranes）Alkali lignin is retained out, and reclaims the alkali lye of dialysis, alkali lignin is acidified to obtain lignin suspension with dilute sulfuric acid, and agitated sedimentation excludes silt, centrifugal filtration（Or press filtration）, pickling and deionized water washing etc. operation, obtain the lignin of purifying.This method eliminates the major pollutants of black liquid, isolates the lignin and hemicellulose of high added value, also achieves recycling for alkali lye, it is few with acid amount, and can be recycled, realize zero-emission, or very small amount is discharged, operating cost is low, there is very high Social benefit and economic benefit.
Description
Technical field
The present invention relates to environmental protection and resource recycling field, more particularly to one kind is from black liquid separating lignin and partly
Cellulose and the method for reclaiming alkali lye.
Background technology
The paper industry of China is mainly raw material using various timber and herbaceous plant, such as willow, pine tree, Chinese fir, eucalyptus,
Reed, wheat straw, straw, cornstalk, corncob, bagasse etc..Substantial amounts of stench, the poisonous black liquor of paper industry discharge, it is led
It is the lignin that hemicellulose and microorganism can not be metabolized to want composition, it is estimated that, the lignin that China's paper industry is discharged every year
Up to 40,000,000 tons.The main method of processing black liquid is to mix burn-up with the coal dust in power plant after concentrating at present.China's mesh
The preceding lignin for still having more than 95% and hemicellulose are discharged with undressed black liquid, are the maximums of China's Inland Water
One of pollution sources.On the other hand, the alkali lye contained in black liquid is the necessary raw material of paper industry, lignin and hemicellulose
It is the raw material of many high value added products.Hemicellulose contains various saccharides material, including D- xylosyls, D-MANNOSE base, D-
Glucosyl group, D- galactosyls, L-arabinose base, 4-O- methyl-D-glucose aldehydic acid bases, D- galacturonics acidic group and D- Portugals
Grape alditol acidic group etc., also a small amount of L- rhamnoses, L-fucose etc..Later research in 2010 finds that lignin is that manufacture is high
The valable starting materials of strong engineering plastics, carbon fiber and graphene, added value is high.Therefore from papermaking night separate hemicellulose and
High Vinsol, and alkali lye is reclaimed, pollution has both been eliminated, has been turned waste into wealth again, has there is very high Social benefit and economic benefit.
Applicant retrieves the pertinent literature of the following method for being separated from black liquid or extracting lignin or alkali：
1st, Chinese patent, application number：201510560992.8；Applicant：Hainan Jinhai Pulp ＆ Paper Co., Ltd.；Invention name
Claim：A kind of black liquor classification separator and its method；Summary：The invention discloses wooden in a kind of black liquid
Quality is classified separator and its method, it is characterised in that this device include black liquor storage tank, the first shifting pump, pretreatment unit,
First film filter, the second film filter, tertiary membrane filter, polymer wood quality storage tank, membrane filtration liquid storage tank, the second transfer
Pump, the 4th film filter, the 5th film filter, the 6th film filter, connecting tube and low molecule lignin storage tank；The method includes
Following steps：Pretreatment, first time membrane filtration, second of membrane filtration；Using wooden in a kind of black liquid provided by the present invention
Quality is classified separator and its method, can be separated the alkali and lignin in black liquor, alkali can send pulping system back to
Decoction circulation is carried out, the lignin of different molecular weight rank is also may separate out, in being sold or made as different byproducts
Between product reprocessed, the method is simple to operate, and water consume, energy consumption are low, with good prospect.
2nd, Chinese patent, application number：201310082509.0；Applicant：Zhejiang Jie Fa Science and Technology Ltd.s；Invention name
Claim：A kind of method that utilization black liquid prepares lignin；Summary：Prepared the invention discloses one kind using black liquid wooden
The method of element, using black liquid as raw material, is pre-processed to black liquid, removes water-insoluble particle and fibrous impurity；
Recycle film process to remove the organic matter less than lignin molecule amount, obtain concentrate；Then to being carried out in concentrate at acid out
Reason, obtains macromolecular rugose wood element precipitation；Most produce high-purity lignin through the inorganic salts produced by desalination removing acid out afterwards.
Its yield of the method for the present invention is not influenceed by the change of raw material black liquid consistency, and separation and Extraction lignin purity is high, molecular size range
More uniform, removal of impurity is high, and modified sodium lignosulfonate application of dispersant performance is significantly carried made from sulfonated condensation
It is high.
3rd, Chinese patent, application number：200910077742.3；Applicant：Beijing Jiahemu Science and Technology Co., Ltd；Invention name
Claim：The method of extracting lignose from papermaking black liquor；Summary：The present invention relates to the method for extracting lignose from papermaking black liquor.Papermaking
The pollution-free of black liquor utilizes the problem for being puzzlement Paper Industry Development.The present invention adjusts black liquid progress pH to 8-10, leads to
Cross pretreatment system to be pre-processed, remove big suspended particulate and colloidal impurity；Pretreatment system is that a filtering accuracy is 100
Passed through to the mechanical oscillation sieve filter or bag filter of 300 mesh scopes, and a molecular cut off for 200,000-50 ten thousand scopes
Cross modified seperation film；Modified separation membrane material is by bulk graft modification, surface graft modification or alloy modification；By two
Level or more than two grades seperation films carry out refined filtrations, and the molecular cut offs of seperation films at different levels is from 150 to 50000.The invention product
Middle Vinsol's content is not less than 55%, up to more than 90.0% after concentration purification；Heatproof is up to more than 130 DEG C；Apparent ash content
Content is smaller than 5%；And tunable molecular weight size and distribution, produce the lignin product of different qualities；Water can be accomplished simultaneously
Fully recycle.
4th, Chinese patent, application number：85106333；Applicant：Zhang Muen；Denomination of invention：Alkali and wooden in black liquid
The mill by coacervation and precipitation of element；Summary：With alkali and the mill by coacervation and precipitation of lignin in a kind of black liquid, it is used as chemical industry model
Farmland.The present invention is by CaO or Ca (OH)2As coagulation agent, in the aqueous slkali for belonging to black liquor or humic acid, with regard to lignin or corruption can be made
Grow the salt coagulation of acid.Through filtering, gained filtrate is aqueous slkali, and gained precipitation can purify the salt for lignin or humic acid.This hair
It is bright to reclaim alkali, lignin or humic acid can be reclaimed again.
5th, Chinese patent, application number：90104181.5；Applicant：Zhang Muen；Denomination of invention：Handle the poly- of black liquid
Heavy partition method；Summary：A kind of method for being handled black liquid and being recycled.This method is extruded by press master
In Normal juice black liquid, addition 2 ~ 5%（Grams per milliliter）Solid calcium chloride or the useless bleaching liquor of calcium chloride, make lignin coagulation, Ran Houtong
Filter filtering is crossed, solid fraction lignin and sig water is obtained, lignin can be as fuel utilization, and sig water can be in blowback spherical digester
Recycle or reclaim alkali.This method small investment, equipment is simple, and strong adaptability, large, medium and small type paper plant can use, Er Qiecheng
This low, energy consumption is small, can reclaim lignin, can recycle or reclaim again alkali, both administer water pollution, turn avoid air dirty
Dye.
6th, Chinese patent, application number：93111777.1；Applicant：Xi Ping Ju；Denomination of invention：A kind of separated in synchronization papermaking
The method of alkali and lignin etc. in black liquor；Summary：The method of alkali and lignin etc., is related to and makes in a kind of separated in synchronization black liquid
The recycling field of paper black liquor.It is characterized in that：Pretreated black liquid → plus flocculant → carelessization → plus plant amylum.Go
Except the white clay of inorganic matter formation（Mainly include SiO2、CaCO3）, remove up to 95%, reclaim the organic matters such as lignin up to 99%,
The alkali lye left can be recycled directly.Equipment, technique are simple, and operating cost is low.
7th, Chinese patent, application number：201210438097.5；Applicant：Li Zheng；Denomination of invention：In reed black liquid
The extracting method of lignin；Summary：The extracting method of reed black liquor belongs to extraction process technology field, especially
It is related to a kind of extracting method of reed black liquor.The present invention provides a kind of recovery rate high, easy to operate reed
The extracting method of black liquor.The present invention is adopted the following technical scheme that：A certain amount of black liquor is taken, acid for adjusting pH is used
Value, adds ethanol and neutralizes；Suction filtration, pH values are adjusted by filtrate, and suction filtration steams the ethanol in filtrate；Taken out with acid solution wash
The solid particle filtered out, is spontaneously dried.
8th, Chinese patent, application number：201110401577.X；Applicant：Nanjing University；Denomination of invention：One kind, which is extracted, divides
From the device and method of Lignin in Wastewater from Paper-Making Mill；Summary：The invention discloses a kind of dress for extracting separation Lignin in Wastewater from Paper-Making Mill
Put and method, the device mainly includes acid out flocculation zone (8), gear bucket (5) and Disengagement zone (10).Present apparatus collection acid out, disappear
Steep, flocculate in one, close between layout, gear bucket and the acid out flocculation zone of Disengagement zone be flexibly connected and duct setting,
A large amount of lignin in extraction separation black liquid that can be rapidly and efficiently, improve lignin extraction amount；The present invention passes through multiple
Being sufficiently mixed for liquid and black liquid is closed, quickly can go out lignin by acid out, flocculation aid PAM is then added and forms bigger
Flco, so that lignin is preferably separated.Present invention improves the shortcoming of traditional acid-precipitation method, before broader practice
Scape.
9th, Chinese patent, application number：201510561740.7；Applicant：Wuhan Kaibisi Electric Power Equipment Co., Ltd.；Hair
Bright title：A kind of device and method that separating lignin is extracted by black liquid；Summary：The present invention relates to pulping wastewater treatment skill
A kind of art field, and in particular to device and method that separating lignin is extracted by black liquid.The present invention's is carried by black liquid
The device and method of separating lignin is taken to utilize the CO in alkali recovery boiler tail gas2、SO2Black liquor is handled Deng sour gas
Lignin is separated out with precipitation form, although for whole pulping system produce nitrogen, sulphur removing without substantial help,
But a part of nitrogen, oxysulfide part can be made to rest on lignin extraction system, so as to alleviate the load of vent gas treatment, reached
The effect of " treatment of wastes with processes of wastes against one another ", while whole pulping system and being not introduced into new impurity, production technology is not required to do too big adjustment.
Three kinds of main compositions that black liquid contains are lignin（40%）, hemicellulose（30%）With alkali and inorganic reagent
（30%）, they are also main pollutant.Above-mentioned 9 patents on black liquid only separate and reclaimed one kind therein
（Lignin）Or two kinds（Lignin and alkali lye）Composition, the full recovery of three kinds of compositions is realized without a kind of.Above-mentioned patent 1,
2nd, 3 are compared close with the black liquor treatment method of the present invention, but are also had significantly different.Patent 1 employs 6 grades of film filters, dams
What is gone out should be the solute alkali lignin in black liquor, expect lignin, also carry out stage acidizing and filtering to alkali lignin,
Not only equipment is complicated, and cost is also very high.Patent 2 has filtered out the organic matter less than lignin molecule amount only with one-level membrane filtration
And alkali lye, but substantial amounts of molecular weight is more than the hemicellulose of lignin（Account for 30%）It is not separated.Patent 3 is first adjusted black liquor
To pH=8-10, now there are a considerable amount of alkali lignins to be transformed into lignin suspension and separated, used moto-vibro screen
Filter or bag filter pretreatment can cause the loss of lignin, then use 2 grades or more than 2 grades UF membranes, retain out
Should be alkali lignin, do not mention alkali lignin acidifying reclaim, do not mention yet recycle of alkali liquor and hemicellulose separation and return
The problem of receipts.Remaining 6 patent（4-9）The method of use is different from the present invention, has only reclaimed one or two kinds of compositions.This hair
It is bright to realize the separation and recovery of three kinds of compositions, not only high financial profit, and eliminate all contaminants in black liquor, we
Method has especially done purification process to lignin, eliminates hemicellulose therein（The organic matters such as carbohydrate）It is miscellaneous with inorganic matter
Matter, is particularly suitable for doing the raw material of carbon fiber and graphene.
The content of the invention
The purpose of the present invention isolates hemicellulose and high Vinsol in being the black liquor discharged from alkali paper-making factory, is used as
The raw material of high value added product, and alkali lye is reclaimed, recycled for paper mill.
Separating lignin and hemicellulose and the method for reclaiming alkali lye from black liquid, producing process include following step
Suddenly：
（1）Black liquid is placed in separation container, undissolved suspension is removed with screen cloth, is settled 4 hours after stirring,
Lower floor's silt is discharged again；
（2）Black liquid first order ultrafiltration, retains and reclaims hemicellulose；
（3）The ultrafiltration of the black liquid second level, retains alkali lignin, and reclaim alkali lye；
（4）Alkali lignin is acidified, and separates out lignin；The alkali lignin of retention is put into acidifier, mass concentration is added
It is acidified, and is stirred continuously for 5 ~ 10% sulfuric acid, regulation to pH=2.5 ~ 3 the cotton-shaped lignin suspended occurs in solution；
（5）Lignin suspension stood 3 hours through mechanical agitation 1 hour, discharge lower floor silt；
（6）Centrifuge or Filter Press；Lignin suspension is injected into centrifuge or Filter Press, the acid solution filtered out
Return to step（4）Recycle；
（7）Lignin pickling and washing；The lignin mass concentration filtered out in centrifuge or filter press for 3% it is dilute
Sulfuric acid is washed 2 times, then is washed with deionized water 3 times, removes the various inorganic ions wherein remained；
（8）Pure lignin is dried.
The black liquor in described paper mill includes various wood pulp black liquor and draft black liquor, and its active ingredient is black liquor
In lignin, hemicellulose and alkali lye.
Described first order ultrafiltration is that pretreated black liquor enters first order ultrafilter, public 2 ~ 3 using ceramic filtration membrane
Filtered under the pressure of jin/square centimeter, trapped substance is hemicellulose, and hemicellulose is washed with deionized 3 times, in 90 DEG C of bakings
Case is dried 3 hours, obtains pure hemicellulose, is put into vacuum bag preservation；It is alkali lignin solution through liquid.
Described second level ultrafiltration be will transmit through liquid injection second level ultrafilter, using ceramic filtration membrane 15 ~ 20 kilograms/
Filtered under the pressure of square centimeter, trapped substance is alkali lignin, is alkali lye through liquid, wherein containing chemical reagent and small molecule thing
Matter, puts storage in tank, or directly return to paper mill.
It is that the lignin that will be filtered out is placed in drying baker that described pure lignin, which is dried, and 3 are dried at a temperature of 90 DEG C
After hour, vacuum packaging obtains pure lignin.
The molecular weight of the ceramic filtration membrane of described first order ultrafilter is 15KD ~ 25KD.
The molecular weight of the ceramic filtration membrane of described second level ultrafilter is 1KD ~ 5KD.
Compared with prior art, the positive effect of the present invention is：
1st, the present invention realizes lignin, the double back receipts of hemicellulose and the recycling for alkali lye in papermaking night, both
The all contaminants of black liquor are eliminated, whole resources therein are taken full advantage of again, being one has important social benefit and economy
The work of benefit, plays the effect turn waste into wealth, turn a crude essay into a literary gem, turning the foul and rotten into the rare and ethereal.Though existing Black Liquor Concentration combustion method energy
Alkali lye is reclaimed, but has burnt up the resource lignin and hemicellulose of preciousness.Though general Ligno-Boost methods can be separated in the world
Lignin, but hemicellulose can not be separated and alkali lye is reclaimed.
2nd, the step of black liquor treatment method of the present invention（3）（Second level ultrafiltration）Just recycle of alkali liquor and convey paper plant circulation make
With subsequent step（4）A small amount of sulfuric acid is used only in alkali lignin acidifying, and can recycle, and row is needed if any spent acid
Put, discharged after being neutralized with a small amount of alkali lye of recovery, secondary pollution is not produced substantially.And international Ligno-Boost
Method can not reclaim alkali lye, also not separate and reclaim hemicellulose.
3rd, in the inventive method, step（2）Pretreated black liquor enters first order ultrafilter, is using molecular weight
15KD-25KD ceramic filtration membrane, is filtered under 2 ~ 3 kilograms of pressure, and the purpose is to the thing that molecular cut off is more than 15KD-25KD
Matter, its trapped substance is mainly hemicellulose, and the liquid less than molecular weight 15KD-25KD is then passed through, and is that alkali is wooden through liquid
Plain solution.Step（3）Liquid injection second level ultrafilter is will transmit through, using the ceramic filtration membrane that molecular weight is 1KD-5KD, 15 ~
Filtered under 25 kilograms of pressure, the purpose is to retain alkali lignin, through mainly containing various chemical reagent and small-molecule substance
Alkali lye.
4th, in black liquor treatment method of the present invention, step（4）Using only a small amount of acid alkali lignin solution can be acidified to pH=
2.5 ~ 3, it is recycled more than 95% lignin.The international Ligno-Boost methods of contrast, use carbon dioxide（CO2）
It is only capable of making alkali lignin be acidified to pH=9.0, lignin can not be recycled fully.
5th, lignin and hemicellulose are separated respective recovery by method of the invention, thus lignin and hemicellulose are all
Purer, particularly lignin is then passed through centrifuging and pickling, washing, quality is more by second level hyperfiltration treatment
Plus it is pure.
Brief description of the drawings
The FB(flow block) of Fig. 1 the inventive method；
The scanning electron microscopy structure for the hemicellulose that Fig. 2 the inventive method is isolated；
The SEM structure charts for the lignin that Fig. 3 the inventive method is isolated.
Embodiment
The inventive method is described in detail below in conjunction with accompanying drawing, the given examples are served only to explain the present invention, not used
In restriction the scope of the present invention.
Embodiment 1
The present embodiment takes 20 liters of willow alkali paper-making black liquor, using listed by present invention step separate hemicellulose and
Lignin, and reclaim alkali lye.Specific producing process is as follows：
Separating lignin and hemicellulose and the method for reclaiming alkali lye from black liquid, producing process include following step
Suddenly：
（1）By paper making with poplar black liquor, 20 liters are placed in separation container, and undissolved suspension is removed with screen cloth, are sunk after stirring
Drop 4 hours, then discharge lower floor's silt；
（2）Black liquid first order ultrafiltration, retains and reclaims hemicellulose；
（3）The ultrafiltration of the black liquid second level, retains alkali lignin, and reclaim alkali lye；
（4）Alkali lignin is acidified, and separates out lignin；The alkali lignin of retention is put into acidifier, mass concentration is added
It is acidified, and is stirred continuously for 5 ~ 10% sulfuric acid, regulation to pH=2.5 ~ 3 the cotton-shaped lignin suspended occurs in solution；
（5）Lignin suspension stood 3 hours through mechanical agitation 1 hour, discharge lower floor silt；
（6）Centrifuge is filtered；By the injection centrifuge filtering of lignin suspension, the acid solution return to step filtered out（4）Circulation
Use；
（7）Lignin pickling and washing；The lignin mass concentration filtered out in centrifuge is 3% dilute sulfuric acid dip 2
It is secondary, then be washed with deionized water 3 times, remove the various inorganic ions wherein remained；
（8）Pure lignin is dried.
Described first order ultrafiltration be pretreated black liquor enter first order ultrafilter, using ceramic filtration membrane 2 kilograms/
Filtered under the pressure of square centimeter, trapped substance is hemicellulose, and hemicellulose is washed with deionized 3 times, in 90 DEG C of baking ovens
Dry 3 hours, obtain 300 grams of pure hemicellulose, be put into vacuum bag preservation；It is alkali lignin solution through liquid.
Described second level ultrafiltration is to will transmit through liquid injection second level ultrafilter, using ceramic filtration membrane 15 kilograms/it is flat
Filtered under square centimetre of pressure, trapped substance is alkali lignin, is alkali lye through liquid, put storage in tank, or directly return to papermaking
Factory.
It is that the lignin that will be filtered out is placed in drying baker that described pure lignin, which is dried, and 3 are dried at a temperature of 90 DEG C
After hour, vacuum packaging obtains pure 550 grams of lignin.
The molecular weight of the ceramic filtration membrane of described first order ultrafilter is 20KD.
The molecular weight of the ceramic filtration membrane of described second level ultrafilter is 3KD.
The scanning electron microscopy of the hemicellulose of the gained of embodiment 1（SEM）Structure is as shown in Fig. 2 be loose many hollow structures.
Fig. 3 is the outside drawing of the lignin of the gained of embodiment 1, is khaki color powder.
Embodiment 2
The present embodiment takes 20 liters of Wheat Straw Alkaline black liquid, using listed by present invention step separate hemicellulose and
Lignin, and reclaim alkali lye.Specific producing process is as follows：
（1）By black liquid generated by making paper with wheat straws, 20 liters are placed in separation container, and undissolved suspension is removed with screen cloth, are sunk after stirring
Drop 4 hours, then discharge lower floor's silt；
（2）Black liquid first order ultrafiltration, retains and reclaims hemicellulose；
（3）The ultrafiltration of the black liquid second level, retains alkali lignin, and reclaim alkali lye；
（4）Alkali lignin is acidified, and separates out lignin；The alkali lignin of retention is put into acidifier, mass concentration is added
It is acidified, and is stirred continuously for 5 ~ 10% sulfuric acid, regulation to pH=2.5 ~ 3 the cotton-shaped lignin suspended occurs in solution；
（5）Lignin suspension stood 3 hours through mechanical agitation 1 hour, discharge lower floor silt；
（6）Centrifuge is filtered；By the injection centrifuge filtering of lignin suspension, the acid solution return to step filtered out（4）Circulation
Use；
（7）Lignin pickling and washing；The lignin mass concentration filtered out in centrifuge is 3% dilute sulfuric acid dip 2
It is secondary, then be washed with deionized water 3 times, remove the various inorganic ions wherein remained；
（8）Pure lignin is dried.
Described first order ultrafiltration be pretreated black liquor enter first order ultrafilter, using ceramic filtration membrane 2 kilograms/
Filtered under the pressure of square centimeter, trapped substance is hemicellulose, and hemicellulose is washed with deionized 3 times, in 90 DEG C of baking ovens
Dry 3 hours, obtain 450 grams of pure hemicellulose, be put into vacuum bag preservation；It is alkali lignin solution through liquid.
Described second level ultrafiltration is to will transmit through liquid injection second level ultrafilter, using ceramic filtration membrane 15 kilograms/it is flat
Filtered under square centimetre of pressure, trapped substance is alkali lignin, is alkali lye through liquid, put storage in tank, or directly return to papermaking
Factory.
It is that the lignin that will be filtered out is placed in drying baker that described pure lignin, which is dried, and 3 are dried at a temperature of 90 DEG C
After hour, vacuum packaging obtains pure 450 grams of lignin.
The molecular weight of the ceramic filtration membrane of described first order ultrafilter is 20KD.
The molecular weight of the ceramic filtration membrane of described second level ultrafilter is 3KD.
Because the content of lignin of wheat straw is less than the content of lignin of poplar, the hemicellulose level of wheat straw is higher than poplar
Hemicellulose level, so the hemicellulose level that embodiment 2 is obtained is higher than poplar, and content of lignin is less than poplar.
Embodiment 3
The present embodiment takes 20 liters of eucalyptus alkali paper-making black liquor, using listed by present invention step separate hemicellulose and
Lignin, and reclaim alkali lye.Specific implementation process is as follows：
（1）By eucalyptus black liquid, 20 liters are placed in separation container, and undissolved suspension is removed with screen cloth, are sunk after stirring
Drop 4 hours, then discharge lower floor's silt；
（2）Black liquid first order ultrafiltration, retains and reclaims hemicellulose；
（3）The ultrafiltration of the black liquid second level, retains alkali lignin, and reclaim alkali lye；
（4）Alkali lignin is acidified, and separates out lignin；The alkali lignin of retention is put into acidifier, mass concentration is added
It is acidified, and is stirred continuously for 5 ~ 10% sulfuric acid, regulation to pH=2.5 ~ 3 the cotton-shaped lignin suspended occurs in solution；
（5）Lignin suspension stood 3 hours through mechanical agitation 1 hour, discharge lower floor silt；
（6）Filter Press；Lignin suspension is injected into Filter Press, the acid solution return to step filtered out（4）Circulation
Use；
（7）Lignin pickling and washing；The lignin mass concentration filtered out in filter press is 3% dilute sulfuric acid dip 2
It is secondary, then be washed with deionized water 3 times, remove the various inorganic ions wherein remained；
（8）Pure lignin is dried.
Described first order ultrafiltration be pretreated black liquor enter first order ultrafilter, using ceramic filtration membrane 3 kilograms/
Filtered under the pressure of square centimeter, trapped substance is hemicellulose, and hemicellulose is washed with deionized 3 times, in 90 DEG C of baking ovens
Dry 3 hours, obtain 350 grams of pure hemicellulose, be put into vacuum bag preservation；It is alkali lignin solution through liquid.
Described second level ultrafiltration is to will transmit through liquid injection second level ultrafilter, using ceramic filtration membrane 18 kilograms/it is flat
Filtered under square centimetre of pressure, trapped substance is alkali lignin, is alkali lye through liquid, put storage in tank, or directly return to papermaking
Factory.
It is that the lignin that will be filtered out is placed in drying baker that described pure lignin, which is dried, and 3 are dried at a temperature of 90 DEG C
After hour, vacuum packaging obtains pure 500 grams of lignin.
The molecular weight of the ceramic filtration membrane of described first order ultrafilter is 15KD.
The molecular weight of the ceramic filtration membrane of described second level ultrafilter is 1KD.
Embodiment 4
The present embodiment takes 20 liters of reed alkali paper-making black liquor, using listed by present invention step separate hemicellulose and
Lignin, and reclaim alkali lye.Specific implementation process is as follows：
（1）By reed black liquid, 20 liters are placed in separation container, and undissolved suspension is removed with screen cloth, are sunk after stirring
Drop 4 hours, then discharge lower floor's silt；
（2）Black liquid first order ultrafiltration, retains and reclaims hemicellulose；
（3）The ultrafiltration of the black liquid second level, retains alkali lignin, and reclaim alkali lye；
（4）Alkali lignin is acidified, and separates out lignin；The alkali lignin of retention is put into acidifier, mass concentration is added
It is acidified, and is stirred continuously for 5 ~ 10% sulfuric acid, regulation to pH=2.5 ~ 3 the cotton-shaped lignin suspended occurs in solution；
（5）Lignin suspension stood 3 hours through mechanical agitation 1 hour, discharge lower floor silt；
（6）Filter Press；Lignin suspension is injected into Filter Press, the acid solution return to step filtered out（4）Circulation
Use；
（7）Lignin pickling and washing；The lignin mass concentration filtered out in filter press is 3% dilute sulfuric acid dip 2
It is secondary, then be washed with deionized water 3 times, remove the various inorganic ions wherein remained；
（8）Pure lignin is dried.
Described first order ultrafiltration be pretreated black liquor enter first order ultrafilter, using ceramic filtration membrane 3 kilograms/
Filtered under the pressure of square centimeter, trapped substance is hemicellulose, and hemicellulose is washed with deionized 3 times, in 90 DEG C of baking ovens
Dry 3 hours, obtain 450 grams of pure hemicellulose, be put into vacuum bag preservation；It is alkali lignin solution through liquid.
Described second level ultrafiltration is to will transmit through liquid injection second level ultrafilter, using ceramic filtration membrane 20 kilograms/it is flat
Filtered under square centimetre of pressure, trapped substance is alkali lignin, is alkali lye through liquid, put storage in tank, or directly return to papermaking
Factory.
It is that the lignin that will be filtered out is placed in drying baker that described pure lignin, which is dried, and 3 are dried at a temperature of 90 DEG C
After hour, vacuum packaging obtains pure 450 grams of lignin.
The molecular weight of the ceramic filtration membrane of described first order ultrafilter is 25KD.
The molecular weight of the ceramic filtration membrane of described second level ultrafilter is 5KD.
Because the content of lignin of reed is less than the content of lignin of eucalyptus, the hemicellulose level of reed is higher than eucalyptus
Hemicellulose level, so the hemicellulose level that embodiment 4 is obtained is higher than eucalyptus, and content of lignin is less than eucalyptus.
Because the raw material sources in each paper mill are different, pulp cooking condition（Temperature, time, concentration of lye etc.）Difference is black
The composition of liquid has difference, and some conditions of the processing method of black liquor of the present invention need regulation in practice, it is most important that
The selection of the filter sizes of two-stage level ultrafiltration.The aperture of the filter membrane of first order ultrafiltration between 15KD to 25KD, second level ultrafiltration
The aperture of filter membrane is between 1KD to 5KD.The first order and the pressure of second level ultrafiltration will also be adjusted according to the character of solution.
Claims (1)
1. separating lignin and hemicellulose and the method for reclaiming alkali lye from black liquid, it is characterised in that：Using paper mill
Black liquor, producing process comprises the following steps：
（1）Black liquid is placed in separation container, undissolved suspension is removed with screen cloth, is settled 4 hours after stirring, row
Put down a layer silt；
（2）Black liquid first order ultrafiltration, retains and reclaims hemicellulose；
（3）The ultrafiltration of the black liquid second level, retains alkali lignin, and reclaim alkali lye；
（4）Alkali lignin is acidified, and separates out lignin；The alkali lignin of retention is put into acidifier, it is 5 to add mass concentration
~ 10% sulfuric acid acidifying, and be stirred continuously, regulation to pH=2. 5 ~ 3, there is the cotton-shaped lignin suspended in solution；
（5）Lignin suspension stood 3 hours through mechanical agitation 1 hour, and lower floor's silt is discharged again；
（6）Centrifuge or Filter Press；Lignin suspension is injected into centrifuge or Filter Press, the acid solution filtered out is returned
Return step（4）Recycle；
（7）Lignin pickling and washing；The lignin mass concentration filtered out in centrifuge or filter press is 3% dilute sulfuric acid
Wash 2 times, then be washed with deionized water 3 times, remove the various inorganic ions wherein remained；
（8）Pure lignin is dried；
The black liquor in described paper mill includes various wood pulp black liquor and draft black liquor, and its active ingredient is in black liquor
Lignin, hemicellulose and alkali lye；
Described first order ultrafiltration is that pretreated black liquor enters first order ultrafilter, using ceramic filtration membrane 2 ~ 3 kilograms/it is flat
Filtered under square centimetre of pressure, trapped substance is hemicellulose, and hemicellulose is washed with deionized 3 times, it is dry in 90 DEG C of baking ovens
Dry 3 hours, pure hemicellulose is obtained, vacuum bag preservation is put into；It is alkali lignin solution through liquid；
Described second level ultrafiltration is to will transmit through liquid injection second level ultrafilter, using ceramic filtration membrane in 15 ~ 25 kilograms/square
Centimetre pressure under filter, trapped substance is alkali lignin, is alkali lye through liquid, containing various chemical reagent and small-molecule substance,
Storage in tank is put, or directly returns to paper mill；
It is that the lignin that will be filtered out is placed in drying baker that described pure lignin, which is dried, is dried 3 hours at a temperature of 90 DEG C
Afterwards, pure lignin is obtained, is vacuum-packed；
The molecular weight of the ceramic filtration membrane of described first order ultrafilter is 15KD ~ 25KD；
The molecular weight of the ceramic filtration membrane of described second level ultrafilter is 1KD ~ 5KD.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610233203.4A CN105714590B (en) | 2016-04-15 | 2016-04-15 | Separating lignin and hemicellulose and the method for reclaiming alkali lye from black liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610233203.4A CN105714590B (en) | 2016-04-15 | 2016-04-15 | Separating lignin and hemicellulose and the method for reclaiming alkali lye from black liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105714590A CN105714590A (en) | 2016-06-29 |
| CN105714590B true CN105714590B (en) | 2017-10-31 |
Family
ID=56161106
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610233203.4A Active CN105714590B (en) | 2016-04-15 | 2016-04-15 | Separating lignin and hemicellulose and the method for reclaiming alkali lye from black liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105714590B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112888747A (en) * | 2018-10-08 | 2021-06-01 | 斯道拉恩索公司 | Method for preparing resin |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT519059B1 (en) * | 2016-09-02 | 2018-07-15 | Andritz Ag Maschf | Method for separating hemicelluloses from biomass digestion process water or spent alkalis |
| CN106676931B (en) * | 2016-12-30 | 2019-01-08 | 海南金海浆纸业有限公司 | A kind of fully separating method of black liquid component |
| JP7163415B2 (en) * | 2018-05-28 | 2022-10-31 | ピアソン キャピタル エンバイロメンタル （ベイジン） リミテッド | Efficient methods and compositions for recovering products from organic acid pretreatment of plant material |
| CN110894247A (en) * | 2018-09-12 | 2020-03-20 | 上海昶法新材料有限公司 | Method for extracting hemicellulose from pulping black liquor |
| SE542795C2 (en) * | 2018-10-08 | 2020-07-07 | Stora Enso Oyj | Process for preparing a resin |
| CN109628507A (en) * | 2018-12-12 | 2019-04-16 | 上海昶法新材料有限公司 | A kind of method that papermaking wastewater prepares lactic acid |
| CN114014957A (en) * | 2021-11-30 | 2022-02-08 | 上海昶法新材料有限公司 | Method for extracting hemicellulose from waste paper |
| CN114044836A (en) * | 2021-11-30 | 2022-02-15 | 上海昶法新材料有限公司 | Method for extracting hemicellulose from chemical pulp |
| CN114687234B (en) * | 2022-03-31 | 2023-06-16 | 华南理工大学 | Method for preparing fluff pulp by utilizing bamboo and fluff pulp prepared by same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5771690A (en) * | 1980-10-22 | 1982-05-04 | Sanyo Kokusaku Pulp Co Ltd | Treating method for waste liquid of kraft pulp |
| CN101402500A (en) * | 2008-11-18 | 2009-04-08 | 中南大学 | Film treatment method for black liquor from papermaking |
| CN103145998B (en) * | 2013-03-15 | 2015-06-10 | 浙江捷发科技有限公司 | Method for preparing lignin by utilizing papermaking black liquid |
| CN104153232A (en) * | 2014-08-06 | 2014-11-19 | 广西星岛科技发展有限公司 | Method for treating pulping black liquor through alkali cooking method taking gramineous plants as materials |
-
2016
- 2016-04-15 CN CN201610233203.4A patent/CN105714590B/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112888747A (en) * | 2018-10-08 | 2021-06-01 | 斯道拉恩索公司 | Method for preparing resin |
| CN112888747B (en) * | 2018-10-08 | 2023-03-14 | 斯道拉恩索公司 | Method for preparing resin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105714590A (en) | 2016-06-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105714590B (en) | Separating lignin and hemicellulose and the method for reclaiming alkali lye from black liquid | |
| CN102677515B (en) | Process for preparing recovered pulp with high whiteness and high cleanliness | |
| CN101736638B (en) | Processing method of paper-making pulping black liquor | |
| CN102363930B (en) | Method for preparing active carbon during alkali recovery of papermaking black liquor | |
| CN101805077B (en) | Treating method of paper-making water recycling use in the production process of reconstituted tobacco | |
| CN106191328A (en) | A kind of xylose production process | |
| CN101402500A (en) | Film treatment method for black liquor from papermaking | |
| CN101948192A (en) | Membrane technology-based papermaking black liquor high-efficiency comprehensive treatment method | |
| CN106219826B (en) | Grading treatment and cascade recycling system and method for white water of paper-making reconstituted tobacco | |
| CN104674590B (en) | The processing method and its processing equipment of black liquid | |
| CN102877350A (en) | Black liquor treatment method by lignin extraction and alkali recovery | |
| KR20080100169A (en) | System and method for the renovation of process water | |
| CN101798768B (en) | Waste paper regeneration environmental protection device and method | |
| US20080251374A1 (en) | System and method for producing ethanol from paper mill sludge | |
| CN102351364B (en) | Treatment method of wood chip washing waste water | |
| CN1962686A (en) | Method for cleanly producing saponin by integrated utilization of yam | |
| CN100500991C (en) | Process for reclaiming and comprehensively utilizing waste digestion liquid of alkaline (or neutral) straw pulp generated by sodium sulfite method | |
| CN106348429A (en) | Kudzuvine root resource utilization method for flavonol, starch and amino acid separation and purification | |
| CN102633405A (en) | Treatment method of papermaking black liquor | |
| JP3927120B2 (en) | Method for recovering inorganic substances from deinked sludge | |
| CN106702804B (en) | A kind of method that lignin is extracted in black liquor | |
| CN103015246A (en) | Method for comprehensively using pulping waste water by sulfite method | |
| CN108245992B (en) | Centrifugal filtration method of cane sugar factory mud juice | |
| CN207016648U (en) | A kind of purified cotton cooking sewage disposal reuse means | |
| CN1587077A (en) | Process for extracting lignin by acid separation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |